Biocompatible and biodegradable polymer hydrogels are useful carriers for delivering active agents and cells for biomedical applications, such as in tissue engineering and controlled drug release. Purified native silk fibroin protein forms β-sheet-rich crosslinked hydrogel structures from aqueous solution, with the mechanics of the process and gel properties influenced by environmental parameters. Traditional gelation methods using aqueous native silk protein solutions, under physiologically relevant conditions, often range from days to weeks for gelation: too slow for the incorporation of cells and labile active agents. High temperature, low pH, or high ionic strength may reduce the gelation time to a few hours, but these conditions may potentially alter cell or bioactive molecule function and limit cell viability. Moreover, biological and some physical properties of silk hydrogel scaffolds are crucial for cell encapsulation/delivery applications. For example, hydrogelation kinetics should be controlled to enable homogeneous 3-dimensional (3-D) encapsulation of cells/active agents and prevention of cell/active agent sedimentation. The ease of application of hydrogel/active molecules scaffolds into the target cite with high spatial precision is also of practical consideration for encapsulation/delivery applications. Thus, there remains need in the art for a process of initiating silk fibroin gelation at mild physiological conditions, with controllable kinetics and properties of the silk hydrogel, as well as the delivery of the gels with spatial precision.